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use of captured CO2 from power plants and heavy industries to synthesise FA can potentially reduce the emissions from the energy and transport sectors. 5.3 Formic acid CDU process simulation in CHEMCAD The chemical catalysis has been selected instead of the electrochemical route taking into account that, in general, chemical catalysis has been performed for more years. The process considered for the production of FA from captured CO2 is based on a homogeneous catalysis and the layout follows the process described in the patent from Schaub et al. [130], specifically, in Figure 2 from the mentioned patent. To the best of our knowledge, this is the most detailed source found in public bibliography. It is assumed that the plant, at full market scale, works under the same conditions as the ones reported for the laboratory tests from [130]. The efficiencies, as calculated from the values stated in the patent, have been used to calibrate and validate the CHEMCAD model. The selected values to perform our process model belong to examples A-12, B-3, D-1a and D-1b. The selected scale for modelling is lower than the average scale for the conventional FA synthesis plant, taking into account also the existence of smaller electrochemical plants, as summarised in the previous section. The synthesis process can be divided into five sections: (i) compression stage, (ii) reaction stage, (iii) liquid-liquid separation stage for catalysts recovery, (iv) stripping stage for methanol recovery, and finally, (v) reactive distillation stage for the formation and purification of the FA product. The plant is designed to produce 1 500 kg/h (12 kt/yr) of FA at a purity of 85 wt % diluted in methanol. Therefore, 1 260 kg/h of CO2 and 90 kg/h of H2 are required as feed. In the reactor, the two main streams react in the presence of two catalysts (ruthenium- and phosphino-based catalysts), a tertiary amine, and a polar solvent (made by a mixture of methanol and water); all of them composing the group of consumables, to form a FA-amine adduct, which has to be thermically separated to provide FA in the last distillation step. The two catalysts and the tertiary amine have been introduced into the software based on the information from Sigma-Aldrich and ChemSpider websites [152]–[154]. The properties of the amine and the adduct (a combination of one mole of FA + one mole of amine) have been estimated in CHEMCAD with the Elliot group contribution method [155]. The process is modelled in CHEMCAD using the Predictive Soave-Redlich-Kwong (PSRK) method for equilibrium and property calculation. The PSRK subgroup parameters have been taken from the UNIFAC consortium parameter set distributed in 2015 [156]. Due to uncertainties in the thermodynamic model at the pressures of the process (up to 105 bar), conversion and consumption figures have been estimated, in addition, from the patent [130]. Figure 13 shows the process flow diagram of the simulated process, and the different stages are explained in the following lines. 5.3.1 Compression stage (Units 1-13) The CO2 feed stream coming at atmospheric pressure and ambient temperature (stream 1), is compressed in a five-stage compression system up to 105 bar (units 1, 3, 5, 7, 9). It is cooled down to 25 °C in the intermediate cooling stages (units 2, 4, 6, 8) and to 30 °C in the after cooler (unit 10), that is condensing the CO2 stream going to the reactor. The compressors are assumed to operate at an isentropic efficiency of 75 % which leads to an electricity consumption of 130 kW. The H2 feed stream enters the process at 30 bar and ambient temperature (stream 12), coming from the electrolyser. It is compressed in two steps, up to 105 bar, consuming 35 kW of electricity (units 11 and 13, with intermediate cooling, unit 12). In the electrolyser, a stream of 900 kg/h of water is needed. The electrolyser consumes 5.7 MW of electricity, and produces the required H2 and 47PDF Image | evaluation of CO2 utilisation for fuel production
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